Bridging cationic complexes

In the case of tungsten, the terephthalate-bridged cationic complex shows EPR spectra consistent with delocalization over all four W atoms [48]. 

Similarly, when both the Cp and arene ligands are permethylated, the reaction of 02 with the Fe1 complex leads to C-H activation of the more acidic benzyl bond [57]. When no benzylic hydrogen is present, superoxide reacts as a nucleophile and adds onto the benzene ligand of the FeCp(arene)+ cation to give a peroxocyclohexadienyl radical which couples with a Fe Cp(arene) radical. A symmetrical bridging peroxo complex [(Fe"Cp)2(r 5-C6H60)2] is obtained. The C-H activation reactions of the 19e Fe1 radicals BH can be summarized as follows... 

The reaction of the coordinatively unsaturated ruthenium amidinates with [Cp RuCl]4 tetramer or [CpRufMeCNlsJPFg provides access to novel amidinate-bridged dinuclear ruthenium complexes (Scheme 146), which in turn can be transformed into cationic complexes or hydride derivatives. In these complexes, a bridging amidinate ligand perpendicular to the metal-metal axis effectively stabilizes the highly reactive cationic diruthenium species. 

Fig. 26. (a) A stereoview of the hydroxide-bridged complex and (b) the crystal structure (93) of the complex cation CudIXOHXO-BISTREN), showing the hydrogen bonding that appears to promote formation of the bridged hydroxy complex. 

FABMS has shown that the bulky Pr PCEhCHhPPr forms the dimeric [ TcNCl2(P-P) 2]. The 3,PNMR spectrum indicates a chlorine bridged structure [57]. The reaction of MePhNNH2/dppe/[TcOCl4] in MeOH, however, yields a cationic complex formulated as the oxo-imido tra .v-[TcO(NH)(dppe)2]+. Few details are available, but the crystal structure determination showed marked asymmetry in the bonding of the two axial ligands [74]. A distinction between the [HN=Tc=OJ+ core and the tautomeric [N=Tc-OH]+ core should be possible... 

Numerous adsorption complexes of CO and AN in Na-A and in Na-FER were investigated only some of these adsorption complexes (giving an example of each type) are summarized in Table 1. First we discuss the effect from the top due to the interaction with the secondary cation(s). The CO molecule adsorbs on the primary cation (via C end) and when the secondary extra-framework cation is at a suitable distance from the primary cation CO forms a bridged adsorption complex between the... 

The effect from the top is behind the differences in IR spectra of CO adsorbed on various Na-zeolites (Fig. 1). The IR spectrum of CO adsorbed on the high-silica Na-FER shows only one band (centred at 2175 cm 1) that is due to the carbonyl complexes formed on isolated Na+ sites. When the content of Na+ in the sample increases (Na-FER with Si/Al=8), in addition to the band at 2175 cm 1 a new band at 2158 cm"1 appears due to the formation of linearly bridged carbonyl complexes on dual cation sites. The IR spectrum of CO adsorbed on Na-A,which has a large concentration of Na+ cations, shows bands centred at 2163, 2145, and 2129 cm 1 the band at 2163 cm"1 is due to the carbonyl species formed on dual cation sites, while bands at 2145 and 2129 cm"1 are due to carbonyls formed on multiple cation sites (Table 1), i.e., on adsorption sites involving more than two cations. 

Combination of IR spectroscopy and DFT calculations provides evidence that heterogeneous dual cation sites can be formed in zeolites. Bridged carbonyl complexes can be formed whenever two metal cations are at the right distance apart from each other and give rise to a low energy CO stretching band in IR spectra. 

A pinacol-type silylative dimerization of various aromatic aldehydes promoted by a cationic thiolate-bridged diruthenium complex has been reported by Flidai and co-workers (Equation (28)).344 l,2-Diaryl-l,2-disiloxyethanes 153 were isolated as the major products along with the corresponding arylmethyl silyl ethers as minor products. 

Cation binding, in supramolecular chemistry, 24 40-43 Cation bridging, 11 634-635 Cation complexation, routes to, 24 41 Cation exchange, in zeolites, 16 826 Cation-exchange catalysts, 10 477-478 12 191... 

The activity of CMe2-bridged Zr(II) and Hf(II) boratabenzene cationic complexes toward ethylene trimerization has been explored computationally using a gradient-corrected DFT approach the Zr species was calculated to be a highly efficient catalyst, exceeding the efficiency of the corresponding Cp system.108... 

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